Peculiar Atomic Bond Nature in Platinum Monatomic Chains.

Metal atomic chains have been reported to change their electronic or magnetic properties by slight mechanical stimulus. However, the mechanical response has been veiled because of lack of information on the bond nature. Here, we clarify the bond nature in platinum (Pt) monatomic chains by our in situ transmission electron microscope method. The stiffness is measured with sub-N/m precision by quartz length-extension resonator. The bond stiffnesses at the middle of the chain and at the connection to the base are estimated to be 25 and 23 N/m, respectively, which are higher than the bulk counterpart. Interestingly, the bond length of 0.25 nm is found to be elastically stretched to 0.31 nm, corresponding to a 24% strain. Such peculiar bond nature could be explained by a novel concept of "string tension". This study is a milestone that will significantly change the way we think about atomic bonds in one-dimension.

Ring population statistics in an ice lattice model.

We calculate the distribution probability of hexagonal six-site rings in the disordered state of a cubic or hexagonal ice lattice model with ice rules perfectly obeyed. The mean-field distribution obtained is in significant agreement with those, slightly different among them, obtained by Monte Carlo simulations of the cubic or hexagonal model. The results are discussed in connection with the equilibrium and non-equilibrium transition from disorder to ferroelectric proton order.

Frictional lubricity enhanced by quantum mechanics.

The quantum motion of nuclei, generally ignored in the physics of sliding friction, can affect in an important manner the frictional dissipation of a light particle forced to slide in an optical lattice. The density matrix-calculated evolution of the quantum version of the basic Prandtl-Tomlinson model, describing the dragging by an external force of a point particle in a periodic potential, shows that purely classical friction predictions can be very wrong. The strongest quantum effect occurs not for weak but for strong periodic potentials, where barriers are high but energy levels in each well are discrete, and resonant Rabi or Landau-Zener tunneling to states in the nearest well can preempt classical stick-slip with nonnegligible efficiency, depending on the forcing speed. The resulting permeation of otherwise unsurmountable barriers is predicted to cause quantum lubricity, a phenomenon which we expect should be observable in the recently implemented sliding cold ion experiments.

Ballistic thermophoresis of adsorbates on free-standing graphene.

The textbook thermophoretic force which acts on a body in a fluid is proportional to the local temperature gradient. The same is expected to hold for the macroscopic drift behavior of a diffusive cluster or molecule physisorbed on a solid surface. The question we explore here is whether that is still valid on a 2D membrane such as graphene at short sheet length. By means of a nonequilibrium molecular dynamics study of a test system-a gold nanocluster adsorbed on free-standing graphene clamped between two temperatures [Formula: see text] apart-we find a phoretic force which for submicron sheet lengths is parallel to, but basically independent of, the local gradient magnitude. This identifies a thermophoretic regime that is ballistic rather than diffusive, persisting up to and beyond a 100-nanometer sheet length. Analysis shows that the phoretic force is due to the flexural phonons, whose flow is known to be ballistic and distance-independent up to relatively long mean-free paths. However, ordinary harmonic phonons should only carry crystal momentum and, while impinging on the cluster, should not be able to impress real momentum. We show that graphene and other membrane-like monolayers support a specific anharmonic connection between the flexural corrugation and longitudinal phonons whose fast escape leaves behind a 2D-projected mass density increase endowing the flexural phonons, as they move with their group velocity, with real momentum, part of which is transmitted to the adsorbate through scattering. The resulting distance-independent ballistic thermophoretic force is not unlikely to possess practical applications.

Correlation-Driven Dimerization and Topological Gap Opening in Isotropically Strained Graphene.

The phase diagram of isotropically expanded graphene cannot be correctly predicted by ignoring either electron correlations, or mobile carbons, or the effect of applied stress, as was done so far. We calculate the ground state enthalpy (not just energy) of strained graphene by an accurate off-lattice quantum Monte Carlo correlated ansatz of great variational flexibility. Following undistorted semimetallic graphene at low strain, multideterminant Heitler-London correlations stabilize between ≃8.5% and ≃15% strain an insulating Kekulé-like dimerized (DIM) state. Closer to a crystallized resonating-valence bond than to a Peierls state, the DIM state prevails over the competing antiferromagnetic insulating state favored by density-functional calculations which we conduct in parallel. The DIM stressed graphene insulator, whose gap is predicted to grow in excess of 1 eV before failure near 15% strain, is topological in nature, implying under certain conditions 1D metallic interface states lying in the bulk energy gap.

Synthesis and Raman spectroscopy of a layered SiS2 phase at high pressures.

Dichalcogenides are known to exhibit layered solid phases, at ambient and high pressures, where 2D layers of chemically bonded formula units are held together by van der Waals forces. These materials are of great interest for solid-state sciences and technology, along with other 2D systems such as graphene and phosphorene. SiS2 is an archetypal model system of the most fundamental interest within this ensemble. Recently, high pressure (GPa) phases with Si in octahedral coordination by S have been theoretically predicted and also experimentally found to occur in this compound. At variance with stishovite in SiO2, which is a 3D network of SiO6 octahedra, the phases with octahedral coordination in SiS2 are 2D layered. Very importantly, this type of semiconducting material was theoretically predicted to exhibit continuous bandgap closing with pressure to a poor metallic state at tens of GPa. We synthesized layered SiS2 with octahedral coordination in a diamond anvil cell at 7.5-9 GPa, by laser heating together elemental S and Si at 1300-1700 K. Indeed, Raman spectroscopy up to 64.4 GPa is compatible with continuous bandgap closing in this material with the onset of either weak metallicity or of a narrow bandgap semiconductor state with a large density of defect-induced, intra-gap energy levels, at about 57 GPa. Importantly, our investigation adds up to the fundamental knowledge of layered dichalcogenides.

Smallest Archimedean Screw: Facet Dynamics and Friction in Multiwalled Nanotubes.

We identify a new material phenomenon, where minute mechanical manipulations induce pronounced global structural reconfigurations in faceted multiwalled nanotubes. This behavior has strong implications on the tribological properties of these systems and may be the key to understand the enhanced interwall friction recently measured for boron-nitride nanotubes with respect to their carbon counterparts. Notably, the fast rotation of helical facets in these systems upon coaxial sliding may serve as a nanoscale Archimedean screw for directional transport of physisorbed molecules.

Collective spin 1 singlet phase in high-pressure oxygen.

Oxygen, one of the most common and important elements in nature, has an exceedingly well-explored phase diagram under pressure, up to and beyond 100 GPa. At low temperatures, the low-pressure antiferromagnetic phases below 8 GPa where O2 molecules have spin S = 1 are followed by the broad apparently nonmagnetic ε phase from about 8 to 96 GPa. In this phase, which is our focus, molecules group structurally together to form quartets while switching, as believed by most, to spin S = 0. Here we present theoretical results strongly connecting with existing vibrational and optical evidence, showing that this is true only above 20 GPa, whereas the S = 1 molecular state survives up to about 20 GPa. The ε phase thus breaks up into two: a spinless ε0 (20-96 GPa), and another ε1 (8-20 GPa) where the molecules have S = 1 but possess only short-range antiferromagnetic correlations. A local spin liquid-like singlet ground state akin to some earlier proposals, and whose optical signature we identify in existing data, is proposed for this phase. Our proposed phase diagram thus has a first-order phase transition just above 20 GPa, extending at finite temperature and most likely terminating into a crossover with a critical point near 30 GPa and 200 K.

Kondo conductance across the smallest spin 1/2 radical molecule.

Molecular contacts are generally poorly conducting because their energy levels tend to lie far from the Fermi energy of the metal contact, necessitating undesirably large gate and bias voltages in molecular electronics applications. Molecular radicals are an exception because their partly filled orbitals undergo Kondo screening, opening the way to electron passage even at zero bias. Whereas that phenomenon has been experimentally demonstrated for several complex organic radicals, quantitative theoretical predictions have not been attempted so far. It is therefore an open question whether and to what extent an ab initio-based theory is able to make accurate predictions for Kondo temperatures and conductance lineshapes. Choosing nitric oxide (NO) as a simple and exemplary spin 1/2 molecular radical, we present calculations based on a combination of density functional theory and numerical renormalization group (DFT+NRG), predicting a zero bias spectral anomaly with a Kondo temperature of 15 K for NO/Au(111). A scanning tunneling spectroscopy study is subsequently carried out to verify the prediction, and a striking zero bias Kondo anomaly is confirmed, still quite visible at liquid nitrogen temperatures. Comparison shows that the experimental Kondo temperature of about 43 K is larger than the theoretical one, whereas the inverted Fano lineshape implies a strong source of interference not included in the model. These discrepancies are not a surprise, providing in fact an instructive measure of the approximations used in the modeling, which supports and qualifies the viability of the density functional theory and numerical renormalization group approach to the prediction of conductance anomalies in larger molecular radicals.

Giant frictional dissipation peaks and charge-density-wave slips at the NbSe2 surface.

Understanding nanoscale friction and dissipation is central to nanotechnology. The recent detection of the electronic-friction drop caused by the onset of superconductivity in Nb by means of an ultrasensitive non-contact pendulum atomic force microscope (AFM) raised hopes that a wider variety of mechanical-dissipation mechanisms become accessible. Here, we report a multiplet of AFM dissipation peaks arising a few nanometres above the surface of NbSe2--a layered compound exhibiting an incommensurate charge-density wave (CDW). Each peak appears at a well-defined tip-surface interaction force of the order of a nanonewton, and persists up to 70 K, where the short-range order of CDWs is known to disappear. Comparison of the measurements with a theoretical model suggests that the peaks are associated with local, tip-induced 2π phase slips of the CDW, and that dissipation maxima arise from hysteretic behaviour of the CDW phase as the tip oscillates at specific distances where sharp local slips occur.

Friction boosted by equilibrium misalignment of incommensurate two-dimensional colloid monolayers.

Colloidal two-dimensional monolayers sliding in an optical lattice are of recent importance as a frictional system. In the general case when the monolayer and optical lattices are incommensurate, we predict two important novelties, one in the static equilibrium structure, the other in the frictional behavior under sliding. Structurally, realistic simulations show that the colloid layer should possess in full equilibrium a small misalignment rotation angle relative to the optical lattice, an effect so far unnoticed but visible in some published experimental moiré patterns. Under sliding, this misalignment has the effect of boosting the colloid monolayer friction by a considerable factor over the hypothetical aligned case discussed so far. A frictional increase of similar origin must generally affect other incommensurate adsorbed monolayers and contacts, to be sought out case by case.

Static and dynamic friction in sliding colloidal monolayers.

In a pioneer experiment, Bohlein et al. realized the controlled sliding of two-dimensional colloidal crystals over laser-generated periodic or quasi-periodic potentials. Here we present realistic simulations and arguments that besides reproducing the main experimentally observed features give a first theoretical demonstration of the potential impact of colloid sliding in nanotribology. The free motion of solitons and antisolitons in the sliding of hard incommensurate crystals is contrasted with the soliton-antisoliton pair nucleation at the large static friction threshold F(s) when the two lattices are commensurate and pinned. The frictional work directly extracted from particles' velocities can be analyzed as a function of classic tribological parameters, including speed, spacing, and amplitude of the periodic potential (representing, respectively, the mismatch of the sliding interface and the corrugation, or "load"). These and other features suggestive of further experiments and insights promote colloid sliding to a unique friction study instrument.

Shape and area fluctuation effects on nucleation theory.

In standard nucleation theory, the nucleation process is characterized by computing ΔΩ(V), the reversible work required to form a cluster of volume V of the stable phase inside the metastable mother phase. However, other quantities besides the volume could play a role in the free energy of cluster formation, and this will in turn affect the nucleation barrier and the shape of the nucleus. Here we exploit our recently introduced mesoscopic theory of nucleation to compute the free energy cost of a nearly spherical cluster of volume V and a fluctuating surface area A, whereby the maximum of ΔΩ(V) is replaced by a saddle point in ΔΩ(V, A). Compared to the simpler theory based on volume only, the barrier height of ΔΩ(V, A) at the transition state is systematically larger by a few kBT. More importantly, we show that, depending on the physical situation, the most probable shape of the nucleus may be highly non-spherical, even when the surface tension and stiffness of the model are isotropic. Interestingly, these shape fluctuations do not influence or modify the standard Classical Nucleation Theory manner of extracting the interface tension from the logarithm of the nucleation rate near coexistence.

Size scaling of static friction.

Sliding friction across a thin soft lubricant film typically occurs by stick slip, the lubricant fully solidifying at stick, yielding and flowing at slip. The static friction force per unit area preceding slip is known from molecular dynamics (MD) simulations to decrease with increasing contact area. That makes the large-size fate of stick slip unclear and unknown; its possible vanishing is important as it would herald smooth sliding with a dramatic drop of kinetic friction at large size. Here we formulate a scaling law of the static friction force, which for a soft lubricant is predicted to decrease as f(m)+Δf/A(γ) for increasing contact area A, with γ>0. Our main finding is that the value of f(m), controlling the survival of stick slip at large size, can be evaluated by simulations of comparably small size. MD simulations of soft lubricant sliding are presented, which verify this theory.

A fingerprint of surface-tension anisotropy in the free-energy cost of nucleation.

We focus on the Gibbs free energy ΔG for nucleating a droplet of the stable phase (e.g., solid) inside the metastable parent phase (e.g., liquid), close to the first-order transition temperature. This quantity is central to the theory of homogeneous nucleation, since it superintends the nucleation rate. We recently introduced a field theory describing the dependence of ΔG on the droplet volume V, taking into account besides the microscopic fuzziness of the droplet-parent interface, also small fluctuations around the spherical shape whose effect, assuming isotropy, was found to be a characteristic logarithmic term. Here we extend this theory, introducing the effect of anisotropy in the surface tension, and show that in the limit of strong anisotropy ΔG(V) once more develops a term logarithmic on V, now with a prefactor of opposite sign with respect to the isotropic case. Based on this result, we argue that the geometrical shape that large solid nuclei mostly prefer could be inferred from the prefactor of the logarithmic term in the droplet free energy, as determined from the optimization of its near-coexistence profile.

Frictionless nanohighways on crystalline surfaces.

The understanding of friction at nano-scales, ruled by the regular arrangement of atoms, is surprisingly incomplete. Here we provide a unified understanding by studying the interlocking potential energy of two infinite contacting surfaces with arbitrary lattice symmetries, and extending it to finite contacts. We categorize, based purely on geometrical features, all possible contacts into three different types: a structurally lubric contact where the monolayer can move isotropically without friction, a corrugated and strongly interlocked contact, and a newly discovered directionally structurally lubric contact where the layer can move frictionlessly along one specific direction and retains finite friction along all other directions. This novel category is energetically stable against rotational perturbations and provides extreme friction anisotropy. The finite-size analysis shows that our categorization applies to a wide range of technologically relevant materials in contact, from adsorbates on crystal surfaces to layered two-dimensional materials and colloidal monolayers.

Systematic improvement of classical nucleation theory.

We reconsider the applicability of classical nucleation theory (CNT) to the calculation of the free energy of solid cluster formation in a liquid and its use to the evaluation of interface free energies from nucleation barriers. Using two different freezing transitions (hard spheres and NaCl) as test cases, we first observe that the interface-free-energy estimates based on CNT are generally in error. As successive refinements of nucleation-barrier theory, we consider corrections due to a nonsharp solid-liquid interface and to a nonspherical cluster shape. Extensive calculations for the Ising model show that corrections due to a nonsharp and thermally fluctuating interface account for the barrier shape with excellent accuracy. The experimental solid nucleation rates that are measured in colloids are better accounted for by these non-CNT terms, whose effect appears to be crucial in the interpretation of data and in the extraction of the interface tension from them.

Rattler model of the boson peak at silica surfaces.

Recent experiments unveiled two new aspects of the low-energy excitation spectrum of silica glass--commonly termed as the "boson peak" region. The first is that at low temperature the silica surface exhibits a different, softer boson peak than the bulk. The second is a giant thermal blueshift of the surface boson peak frequency causing it to cross and overcome the bulk peak with increasing temperature. Here we present a simple lattice model that reproduces this behavior in all its aspects. Each site consists of rigid tetrahedral units softly connected so as to be able to rotate anharmonically as "rattlers" in their cages. As shown by simulations, the model dynamics exhibits a boson-like peak, which has lower frequency at the surface where rattlers have a weaker restoring force. Upon heating however the larger angular freedom of surface units allows them to rattle more than in the bulk, leading to a steeper frequency increase similar to experiment.

High-pressure polymeric phases of carbon dioxide.

Understanding the structural transformations of solid CO(2) from a molecular solid characterized by weak intermolecular bonding to a 3-dimensional network solid at high pressure has challenged researchers for the past decade. We employ the recently developed metadynamics method combined with ab initio calculations to provide fundamental insight into recent experimental reports on carbon dioxide in the 60-80 GPa pressure region. Pressure-induced polymeric phases and their transformation mechanisms are found. Metadynamics simulations starting from the CO(2)-II (P4(2)/mnm) at 60 GPa and 600 K proceed via an intermediate, partially polymerized phase, and finally yield a fully tetrahedral, layered structure (P-4m2). Based on the agreement between calculated and experimental Raman and X-ray patterns, the recently identified phase VI [Iota V, et al. (2007) Sixfold coordinated carbon dioxide VI. Nature Mat 6:34-38], assumed to be disordered stishovite-like, is instead interpreted as the result of an incomplete transformation of the molecular phase into a final layered structure. In addition, an alpha-cristobalite-like structure (P4(1)2(1)2), is predicted to be formed from CO(2)-III (Cmca) via an intermediate Pbca structure at 80 GPa and low temperatures (<300 K). Defects in the crystals are frequently observed in the calculations at 300 K whereas at 500 to 700 K, CO(2)-III transforms to an amorphous form, consistent with experiment [Santoro M, et al. (2006) Amorphous silica-like carbon dioxide. Nature 441:857-860], but the simulation yields additional structural details for this disordered solid.